Zn_(1–x)Ca_x(Ti_(0.6)Zr_(0.4))Nb_2O_8陶瓷的微波介电性能
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摘要
采用传统固相反应法制备Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8(x=0.05,0.10,0.20,0.30)微波介质陶瓷,研究了不同Ca~(2+)取代量对Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8陶瓷的物相组成、显微结构及微波介电性能的影响,利用X射线衍射仪、扫描电子显微镜和网络分析仪等对其晶体结构、微观形貌及微波介电性能进行表征。结果表明:Ca~(2+)取代Zn~(2+)会导致Ca Nb_2O_6第二相的形成,且随Ca~(2+)含量的增加,ZnTiNb_2O_8相含量减少;Ca Nb_2O_6相的含量增加,导致Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8陶瓷的介电常数和品质因数减小,谐振频率温度系数向正方向移动。当x=0.3时,Zn_(1-x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8陶瓷在1 140℃烧结并获得最佳微波介电性能:ε_r=30.42,Q×f=47 280 GHz,τ——f=–25.37×10~(–6)/℃。
Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8(x=0.05,0.10,0.20,0.30)microwave dielectric ceramics were prepared by a solid-state reaction method.The effect of Ca~(2+)substitution amount on the phase composition,microstructure and microwave dielectric properties of Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_(8 )ceramics was investigated by X-ray diffraction,scanning electron microscopy and network analysis,respectively.The results show that Ca~(2+)substitution of Zn~(2+)leads to the formation of the second phase of CaNb_2O_6,the content of ZnTiNb_2O_8 phase decreases and the content of CaNb_2O_6 phase increases with the increase of Ca~(2+)content,leading to the decrease of dielectric constantε_r and quality factor Q′f of Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8 ceramics,and the temperature coefficient of resonant frequencyτ_f shifting to a positive direction.The optimum microwave dielectric properties(i.e.,ε_r=30.42,Q′f=47 280 GHz,τ_f=–25.37×10~(–6)/℃) are obtained when Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8 ceramic is sintered at 1 140 ℃ as x=0.3.
Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8(x=0.05,0.10,0.20,0.30)microwave dielectric ceramics were prepared by a solid-state reaction method.The effect of Ca~(2+)substitution amount on the phase composition,microstructure and microwave dielectric properties of Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_(8 )ceramics was investigated by X-ray diffraction,scanning electron microscopy and network analysis,respectively.The results show that Ca~(2+)substitution of Zn~(2+)leads to the formation of the second phase of CaNb_2O_6,the content of ZnTiNb_2O_8 phase decreases and the content of CaNb_2O_6 phase increases with the increase of Ca~(2+)content,leading to the decrease of dielectric constantε_r and quality factor Q′f of Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8 ceramics,and the temperature coefficient of resonant frequencyτ_f shifting to a positive direction.The optimum microwave dielectric properties(i.e.,ε_r=30.42,Q′f=47 280 GHz,τ_f=–25.37×10~(–6)/℃) are obtained when Zn_(1–x)Ca_xTi_(0.6)Zr_(0.4)Nb_2O_8 ceramic is sintered at 1 140 ℃ as x=0.3.
引文
[1]刘庆林,唐斌,李皓,等.Zn0.7Co0.3(Ti1-x Snx)Nb2O8陶瓷微波介电性能研究[J].压电与声光,2015(1):64-67.LIU Qinglin,TANG Bin,LI Hao,et al.Piezo Acoustoopt(in Chinese),2015(1):64-67.
[2]LIN W Y,SPEYER R F,HACKENBERGER W S,et al.Microwave properties of Ba2Ti9O20 doped with zirconium and tin oxides[J].Cheminform,2010,82(5):1207-1211.
[3]LAISHRAM R,GAUR R,SINGH K C,et al.Control of coring effect in Ba Ti4O9 microwave dielectric ceramics by doping with Mn4+[J].Ceram Int,2016,42(4):5286-5290.
[4]PAMU D,RAO G L N,RAJU K C J.Enhanced microwave dielectric properties of(Zr0.8,Sn0.2)TiO4 ceramics with the addition of its own nanoparticles[J].J Am Ceram Soc,2012,95(1):126-132.
[5]KAWASHIMA S,NISHIDA M,UEDA I,et al.Ba(Zn1/3Ta2/3)O3ceramics with low dielectric loss at microwave frequencies[J].J Am Ceram Soc,2010,66(6):421-423.
[6]王利青,刘亚云.Ca TiO3-LaAlO3微波介质陶瓷的研究进展[J].硅酸盐通报,2014,33(1):103-106.WANG Liqing,LIU Yayun.Bull Chin Ceram Soc(in Chinese),2014,33(1):103-106.
[7]KIM D,HONG K S.Phase relations and microwave dielectric properties of ZnNb2O6-TiO2[J].J Mater Res,2000,15(6):1331-1335.
[8]HUANG C L,HUANG S H,LEE R Z.The microwave dielectric materials of(Zn1-x Mgx)TiNb2O8 for electroceramics devices applications[J].Key Eng Mater,2013,547:49-55.
[9]ZHOU D,LI W B,XI H H,et al.Phase composition,crystal structure,infrared reflectivity and microwave dielectric properties of temperature stable composite ceramics(scheelite and zircon-type)in BiVO4-YVO4system[J].J Mater Chem C,2015,3(11):2582-2588.
[10]FANG Z,TANG B,SI F,et al.Temperature stable and high-Qmicrowave dielectric ceramics in the Li2Mg3-x Cax Ti O6,system(x=0.00-0.18)[J].Ceram Int,2017,43(2):1682-1687.
[11]GEORGE S,SEBASTIAN M T.Microwave dielectric properties of novel temperature stable high Q Li2Mg1-x Znx Ti3O8 and Li2A1-x Cax Ti3O8(A=Mg,Zn)ceramics[J].J Eur Ceram Soc,2010,30(12):2585-2592.
[12]LIN Y J,WANG S F,LAI B C,et al.Densification,microstructure evolution,and microwave dielectric properties of Mg1-x Cax ZrTa2O8ceramics[J].J Eur Ceram Soc,2017,37(8):2825-2831.
[13]LEE H J,HONG K S,KIM S J,et al.Dielectric properties of MNb2O6compounds(where M=Ca,Mn,Co,Ni,or Zn)[J].Mater Res Bull,1997,32(7):847-855.
[14]张岭.ZnO-Nb2O5-TiO2系微波介质陶瓷低温烧结特性的研究[D].武汉:华中科技大学,2010.ZHANG Ling.Research on the low-sintering behavior of microwave dielectric ZnO-Nb2O5-TiO2 ceramics(in Chinese,dissertation).Wuhan:Huazhong University of Science and Technology,2010
[15]VALANT M,SUVOROV D,RAWN,C J.Intrinsic reasons for variations in dielectric properties of Ba6-3x R8+2x Ti18O54(R=LA-Gd)solid solutions[J].Jpn J Appl Phys,1999,38:2820-2826.
[2]LIN W Y,SPEYER R F,HACKENBERGER W S,et al.Microwave properties of Ba2Ti9O20 doped with zirconium and tin oxides[J].Cheminform,2010,82(5):1207-1211.
[3]LAISHRAM R,GAUR R,SINGH K C,et al.Control of coring effect in Ba Ti4O9 microwave dielectric ceramics by doping with Mn4+[J].Ceram Int,2016,42(4):5286-5290.
[4]PAMU D,RAO G L N,RAJU K C J.Enhanced microwave dielectric properties of(Zr0.8,Sn0.2)TiO4 ceramics with the addition of its own nanoparticles[J].J Am Ceram Soc,2012,95(1):126-132.
[5]KAWASHIMA S,NISHIDA M,UEDA I,et al.Ba(Zn1/3Ta2/3)O3ceramics with low dielectric loss at microwave frequencies[J].J Am Ceram Soc,2010,66(6):421-423.
[6]王利青,刘亚云.Ca TiO3-LaAlO3微波介质陶瓷的研究进展[J].硅酸盐通报,2014,33(1):103-106.WANG Liqing,LIU Yayun.Bull Chin Ceram Soc(in Chinese),2014,33(1):103-106.
[7]KIM D,HONG K S.Phase relations and microwave dielectric properties of ZnNb2O6-TiO2[J].J Mater Res,2000,15(6):1331-1335.
[8]HUANG C L,HUANG S H,LEE R Z.The microwave dielectric materials of(Zn1-x Mgx)TiNb2O8 for electroceramics devices applications[J].Key Eng Mater,2013,547:49-55.
[9]ZHOU D,LI W B,XI H H,et al.Phase composition,crystal structure,infrared reflectivity and microwave dielectric properties of temperature stable composite ceramics(scheelite and zircon-type)in BiVO4-YVO4system[J].J Mater Chem C,2015,3(11):2582-2588.
[10]FANG Z,TANG B,SI F,et al.Temperature stable and high-Qmicrowave dielectric ceramics in the Li2Mg3-x Cax Ti O6,system(x=0.00-0.18)[J].Ceram Int,2017,43(2):1682-1687.
[11]GEORGE S,SEBASTIAN M T.Microwave dielectric properties of novel temperature stable high Q Li2Mg1-x Znx Ti3O8 and Li2A1-x Cax Ti3O8(A=Mg,Zn)ceramics[J].J Eur Ceram Soc,2010,30(12):2585-2592.
[12]LIN Y J,WANG S F,LAI B C,et al.Densification,microstructure evolution,and microwave dielectric properties of Mg1-x Cax ZrTa2O8ceramics[J].J Eur Ceram Soc,2017,37(8):2825-2831.
[13]LEE H J,HONG K S,KIM S J,et al.Dielectric properties of MNb2O6compounds(where M=Ca,Mn,Co,Ni,or Zn)[J].Mater Res Bull,1997,32(7):847-855.
[14]张岭.ZnO-Nb2O5-TiO2系微波介质陶瓷低温烧结特性的研究[D].武汉:华中科技大学,2010.ZHANG Ling.Research on the low-sintering behavior of microwave dielectric ZnO-Nb2O5-TiO2 ceramics(in Chinese,dissertation).Wuhan:Huazhong University of Science and Technology,2010
[15]VALANT M,SUVOROV D,RAWN,C J.Intrinsic reasons for variations in dielectric properties of Ba6-3x R8+2x Ti18O54(R=LA-Gd)solid solutions[J].Jpn J Appl Phys,1999,38:2820-2826.